JPS6020739B2 - Method for manufacturing silver halide photographic materials - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing a silver halide photographic light-sensitive material, which comprises a silver halide emulsion layer and at least one antistatic layer. The present invention relates to a method for producing a silver photographic material.

In the manufacture and use of photographic materials, static electricity tends to accumulate, and this accumulation of static electricity causes many problems.

This electrification occurs, for example, in the manufacturing process at the contact point between the photographic light-sensitive material and a roller, or when the photographic light-sensitive material is rolled up, rubbed against the support surface and the emulsion surface during the unwinding process, or peeled off. Peeling between the support and the emulsion surface when exposed to temperatures high enough to cause adhesion, as well as film cameras, film cameras, X-ray film, etc. Occur. The photosensitive material is then exposed to light at the point where these accumulated static electricity is discharged, and after the development process, irregular static marks such as spots, twigs, and feathers are formed, which deteriorates the photosensitive material. This results in a significant loss of product value. These static marks are one of the trickiest problems because their existence is not known until they are developed. Further, the accumulated static electricity causes dust to adhere to the surface of the photosensitive material, causing secondary failures such as non-uniform failures during coating.
Furthermore, since all photosensitive material supports are hydrophobic, they accumulate a large amount of static electricity, and the occurrence of static marks increases as the processing speed and emulsion sensitivity increase, resulting in a significant adverse effect. Various substances have been used to prevent charging of photographic materials.

When used, these substances may be used alone or in combination. In order to directly impart antistatic properties to the support of photographic light-sensitive materials, it is known that such substances are directly blended into the polymeric material that is the support, or coated on the surface of the support. There is. For the latter coating, a method is used in which an antistatic agent is applied alone or in combination with a polymeric substance such as gelatin, polyvinyl alcohol, cellulose acetate, polyvinyl formal, or polyvinyl butyral. Further, the antistatic agent can be added not only to the photosensitive emulsion layer provided on the support but also to non-photosensitive auxiliary layers (eg, packing layer, antihalation layer, intermediate layer, protective layer, etc.). Alternatively, there is a method of coating the developed photosensitive material to prevent dust from adhering to the developed photosensitive material during handling. By the way, few of the known antistatic agents show satisfactory effects on the performance of photosensitive materials having high-sensitivity emulsion layers, especially under low humidity conditions, or the antistatic effect deteriorates over time, or when high temperatures or high temperatures are used. It is often accompanied by adhesion failure under humid conditions, and has a ``meh'' effect that adversely affects photographic properties, making it difficult to apply it to photographic light-sensitive materials. Therefore, attempts have been made to apply various different antistatic agents to photographic materials. For example, so-called polymers having a dissociative group in the polymer primary mirror as shown in JP-A-48-191,165, JP-A-49-121,523, JP-A-54-18,728, JP-A-53-92,125, etc. Attempts have been made to apply ionene type polymers to silver halide photographic materials. Although these ionene-type polymers have excellent antistatic properties, they generally have poor film-forming properties, resulting in decreased transparency of the film after coating and poor scratch resistance.

The object of the present invention is to provide a silver halide photographic light-sensitive material provided with an antistatic layer, which has firstly a low surface electrical resistance, secondly has excellent transparency, and thirdly has good adhesion resistance. A manufacturing method is provided. These objects of the present invention include a method for producing a photographic material having at least one light-sensitive silver halide emulsion layer and at least one non-light-sensitive layer, which includes a coating solution for at least one non-light-sensitive layer; Inside, (1
}ionene type polymer and {21} A method for producing an antistatic halogenated synthetic fiber photographic material, which comprises containing at least one compound selected from glycerin, ethylene glycol, propylene glycol, trimethylene glycol, formic acid, and acetamide. achieved by.

The ionene type polymer in the present invention is a polymer having a dissociative group in the main chain, for example, the following general formula (1),
It is a polymer represented by (0) or (m).

(1) In the formula, R and R2 each preferably have 1 to 10 carbon atoms.
alkyl groups, substituted alkyl groups (substituents include, for example, cycloalkyl groups, hydroxyl groups, cyano groups, amido groups, carboxyl groups, alkoxycarponyl groups, carbamyl groups, etc.), cycloalkyl groups, aralkyl groups,
They are aryl groups and alkenyl groups (eg allyl groups).

These R and R2 may be combined with each other to form an alkylene (eg, ethylene). R3 represents an alkylene group or aralkylene group having 10 or less carbon atoms. X, e and x2e each represent an anion, preferably a halogen ion, R40-S02-○-, R4-S02-○-,
(HO)2PO-○- is particularly preferably a halogen ion such as chloride or furomide. n
is about 10 to about 300, preferably about 30 to about 200. (0) In the formula, R5, R6, R7 and R8 are substituted or unsubstituted alkyl groups having 1 to 4 carbon atoms, and A and B each have 1 to 6 carbon atoms.
represents an alkylene group, a methyl hydroxide group, a phenylene group, or a simple bond, and X, e, and x29 represent the general formula (1)
is synonymous with

n represents 10 to 300. (m) In the formula, P and Q each represent straight chain or branched alkylene, xylylene or cyclohexine, and straight chain or branched alkylene has a double bond, triple bond or -(CH2CH20) in the alkylene. It may have y-C4-CH2.

R9, R, o, R, . and R, 2 represent alkyl having 1 to 4 carbon atoms, or R9 and R, . and R,.

and R, 2 may be combined to form a nitrogen-containing heterocycle. X
, e and ×2e have the same meanings as in general formula (1).

n represents an integer of 10 to 300, and y represents an integer of 1 to 20. Compounds represented by general formulas (1), (0) and (m) are respectively
It can be synthesized according to the descriptions in No. 65 and No. 49-121523.

Specific examples of the compounds represented by general formulas (1), (0) and (M) are as follows.

Compound examples >(2> (3) (4) (5> (6) 7) <8) However, the viscosity number refers to 0.1% by weight of ionene type polymer dissolved in 1% by weight of saline solution. This is the value (risp/C) measured at 30 p.m.

In the present invention, the ionene type polymer is incorporated into the silver halide photographic light-sensitive material by coating and drying the coating solution for at least one non-photosensitive layer.

Examples of the non-photosensitive layer include a surface protective layer, an overcoat layer,
Examples include an intermediate layer, an undercoat layer, a back layer, a back overcoat layer, etc., but the effect of the present invention is particularly noticeable in a layer coated with an organic solvent as a non-photosensitive layer. and is, for example, a back layer, a back overcoat layer or a subbing layer.

Examples of the organic solvent used in the non-photosensitive layer coating solution of the present invention include methanol, ethanol, and fluoride.

Ro/gunol, acetone, methyl ethyl ketone, ethyl acetate, butyl acetate, methyl cellosolve, ethyl cellosolve, dioxane, etc. can be used alone or in combination. There is no particular limit to the amount of ionene type polymer contained in the coating solution, and the amount of ionene type polymer contained in the coating solution should be 0.01 to 2 days, particularly 0.05 to 1 day per square meter after coating. However, preferably 0.05 to 5% by weight, especially 0.1 to 2% by weight per coating solution.
Weight%.

In the present invention, at least one non-photosensitive layer coating solution contains at least one compound selected from glycerin, ethylene glycol, propylene glycol, trimethylene glycol, formic acid, and acetamide together with the ionene type polymer. There are characteristics.

Among these compounds, particularly preferred are glycerin, ethylene glycol and acetamide.

It is preferable to use these compounds in a weight ratio of 0.5 to 30 times, particularly 1 to 13 times, the weight of the ionene type polymer.

The coating liquid for the non-photosensitive layer used in the present invention may further include water, a matting agent, a slip agent, a surfactant, a dye,
It can contain gelatin, a gelatin hardening agent, etc.

In particular, when water is used in combination, the effect of the present invention becomes even more remarkable.
20 is preferable.

As the matting agent, silicon dioxide fine particles having an average particle size of 1 to 10 μm are preferable. There are no particular restrictions on the above-mentioned various additives, other additives for the photosensitive silver halide emulsion layer, manufacturing methods, etc. For example, Research Disclosure Magazine 17
The description in Vol. 6, pp. 22-31 (December 1978) can be referred to. Furthermore, the support for the silver halide photographic material of the present invention is not particularly limited, and is based on the above-mentioned research.
Although the description in Disclosure magazine can be referred to, cellulose acetate film and polyethylene terephthalate film are particularly preferred.

The silver halide photosensitive material according to the present invention may be a conventional black-and-white silver halide photosensitive material (for example, a black-and-white photosensitive material for photography,
- monochrome photosensitive materials for rays, monochrome photosensitive materials for printing, etc.), ordinary multilayer color photosensitive materials (e.g., color reversal films, color negative films, color positive films, etc.), and various silver halide photosensitive materials. I can do it.

It is particularly effective for silver halide light-sensitive materials for high-temperature rapid processing and high-sensitivity silver halide light-sensitive materials. The present invention will be further explained below with reference to Examples. Example 1 Preparation of samples: Back layer coating liquids [A] and [B] having the following compositions.
] and 100% each on cellulose triacetate base.
Kawakami/I applied it one by one.

Coating liquid [A] ・Ionene type polymer (compound example-{1)) 8th evening/Wednesday
10 [Glycerin
30 [・methanol
620M acetone
350 [Coating liquid [B]・Ionene type polymer (compound-'1}) 8th evening/Wednesday
8 shout/methanol
650 pine/acetone
350 [A ) and (B) were created.

An indirect radiographic emulsion containing 9% by weight of gelatin and 9% by weight of silver halide was coated on the opposite side of the back layer of the support thus obtained to prepare samples (A) and (B). The surface resistivity of the back layer of samples (A) and (B) is both 1.
Pi○/skin value is shown, but haze value after development processing is sample (
A) was 1.5% while sample (B) was 2.5%.

Example 2 Preparation of samples: Back layer coating liquids [C] and [D] having the following compositions.
] were prepared and coated at 10 [/] each on a polyethylene terephthalate base.

Coating liquid [C]・Ionene type polymer (compound example-{3}) 4th evening/Wednesday
5M methanol
690 Noto/Acetone
300 skin/acetamide 1
0W top coating liquid [D]・Ionene type polymer (compound example-(3}) 4th evening/Wednesday
5 bills/methanol
700 ground/acetone
300 m above each layer, a cellulose diacetate solution was added using a mixed solvent of 600 m of acetone and 300 m of methanol.
/ It was coated to form a pillow to form supports [C] and [D].

A silver halide emulsion was coated on each support in the same manner as in Example 11 to obtain samples (C) and (D).

Claims (1)

[Claims] 1. In a method for producing a photographic material having at least one photosensitive silver halide emulsion layer and at least one non-photosensitive layer, (1) ionene is added to the coating solution for at least one non-photosensitive layer. 1. A method for producing a silver halide photographic material, comprising a type polymer and (2) at least one compound selected from glycerin, ethylene glycol, propylene glycol, trimethylene glycol, formic acid, and acetamide.